Sulphur dyestuffs



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iatented Jan. 23, 1940 UNITED STATES PATENT O C i' SULPHUR DYESTUFFS Werner Zerweck, Frankfort-on-the-Main-Fechenheim, and Wilhelm Hechtenberg, Frankfort- I on-the-Main, Germany, assignors to General Aniline Works, 1110., New York, N. Y., a corporation of Delaware r V V No Drawing. Application August so, 1938, Serial N'o. 227,530. In Germany September 6, 1937 2 Claims.

, 'Our present invention relates to sulphur dyestuffs more particularly to those obtained by actlng withan alkali metal polysulphide on a member of the group consisting of a leucoindophenol of the general formula:

V HOOIIT Ill-l?]ihNHacyl 7 g H X H X wherein R stands for a member of the group consisting of a radicle of the benzene and naphthalene series, R1 for a member of the group consisting of a radicle of the benzene and polynuclear aromatic series, one X for hydrogen and the 15 other X for a member of the group consisting of o Emm ze'r 'Amixture of 15- parts ofthe leucoindophenol from 4-acetylaminodiphenylamine of the formu-.

and a-"polysulphide from 50 parts ofcrystallized s; sodium sulphide, 35 parts of sulphur and 20 parts o' vegetable fibers from a sodium sulphide bath greenish blue shades of good fastness.

Similar dyestuffs are obtained when starting from leucoindophenols derived from 4-methoxyacetylamino-diphenylamine, 4- benzoylaminodi- 4.5 phenylamine, 4-benzenesulfaminodiphenylamine or 4-ortho-carboxybenzoylaminodiphenylamine.

Example 2 A mixture of 15 parts of leucoindophenol de- 50 rived from 4-acetylaminodiphenylamine (as used in Example 1),. 20 parts of anhydrous sodium sulphide, 24 parts of sulphur and about 100 parts of alcohol is boiled for some hours in an apparatus provided with a reflux condenser. The alco- ,5 hol is distilled off vacuo and the dyestufi is parts of water, 20 parts ofcrystallized sodium isolated. The dyestulf thus obtained is, when dry, a blue powder soluble in concentrated sulphuric acid with a, blue color and dyes the vegetable fibers from a sodium sulphide bath very greenish blue shades of a good fastness. 5

, When starting from leucoindophenols derived from lacetylaminodiphenylamines containing in one of the2.3.2- or 3"-'positions a substituent, such as a methyl or methoxy-group or halogen, similar dyestuffs-are obtained. 5 l0 Example 3 A mixtureoflO parts of the leucoindophenol derived from 4- acetylaminophenyl-l-naphthylamine'of the formula: 15

or of the corresponding. indophenol, a polysul- 2o phide from 1'? parts of anhydrous sodium sulphide and 23 parts of sulphur, about 100. parts of butyl alcohol and 6 parts of copper sulphate 'soluble in. concentrated sulphuric acid, with a greenish blue color and dyes the vegetable fibers from a sodium sulphide, bath clear green shades of good fastness.

"Example 4 A mixture of 25: parts of leucoindophenol (or indophenol) from l acetylaminodiphenylamine- 2-carboxylic acid, of the formula:

,HOQNHONHQNHCOGEB coon and an aqueous polysulphide solution from '75 parts of crystallized sodium sulphide and 50 parts of sulphur is boiled for-some hours under reflux. Then the mass is diluted with about 500 sulphide are added and the dyestufi formed is isolated; "It is, when dry, a reddish blue dark fpowder soluble inconcentrated sulphuric acid,

with agreenish blue color. ,It dyes vegetable o fibers from the sodium sulphide bath bright very, greenish'blue shades-of good fastness to light.

' A similar dyestufi is obtained when sulphurizing a leucoindophenol containing chlorine atoms in 'both 'ortho positionsto the, hydroxy group. 35

Example 5 25 parts of the leucoindophenol (or indophenol) from 4-benzoyl aminodiphenylamine-2-carboxylic acid of the formula:

HO-O-NE-O-NHQNHF o 0-6 Example 6 A mixture of the leucoindophenol (or indophenol) from 4 acetylamino-diphenylamine-2- sulphonic acid of the formula:

NHCOCHa with an aqueous polysulphide solution from 120 .parts of crystallized sodium sulphide and parts of sulphur is boiled for a longer time in an apparatus provided with a reflux condenser. After diluting the reaction mass with about 500 parts of water and addition of 30 parts of crystallised sodium sulphide, air is blown in and the dyestufi formed is isolated. It is, when dry, a reddish blue powder soluble in concentrated sulphuric acid with a pure blue color and dyes the vegetable fibers from the sodium sulphide bath greenish blue shades of good fastness to light and a good levelling power.

When starting from the corresponding leucoindophenol derived from 4-benzoylamino-diphenylamine-2-sulphonic acid a similar dyestufi is formed.

Dyestuffs of the same type are obtained when starting from indophenols or leucoindophenols containing a methoxyacetyl radicle or being substituted by alkyl, alkoxy or halogen in one of the 2- or 3 '-positions.

When starting from leucoindophenols derived from 4 benzenesulphoamine diphenylamine- Z-carboxylic or -sulphonic acid, blue dyeing dyestuffs are obtained, when sulfurizing leucoindophenols derived from 5-acetylor -benzoylamino-diphenylamine-z-carboxylic acid, the formed dyestuffs dye the vegetable fiber particularly greenish blue shades of good fastness to light.

Example 7 A mixture of 10 parts ofleucoindophenol- (or indophenol) from N-(d-acetylanfino-Z-carboxyphenyl)-1-naphthylamine of the formula:

23 parts of anhydrous sodium sulphide, 22 parts of sulphur, about parts of butyl alcohol and 6 i parts of copper sulphate is heated for some hours in an apparatus provided With a reflux condenser. The alcohol is distilled off in vacuo and the dyestuff is isolated. It is, when dry, a dark powder,

- soluble in concentrated sulphuric acid with a greenish blue color, and dyes the vegetable fibers from the sodium sulphide bath bright yellowish green shades of good fastness.

When starting from the leucoindophenol derived from 3-benzoylamino-diphenylamine-2'- carboxylic acid the formed sulphur dyestufi dyes the fiber very greenish blue shades of good fastness to light.

Example 8 15 parts of the leucoindophenol derived from N (e-acetylaminophenyl) l-aminonaphthalene- 8-sulphonic acid of the formula:

or the corresponding indophenol, are mixed with an aqueous polysulphide solution, prepared from 45 parts of crystallized sodium sulphide and 30 parts of sulphur and the mixture is heated for some hours at about under reflux. When thedyestufi formation is complete, about 300 parts of water and 15 parts of crystallized sodium sulphide and a small quantity of sodium chloride are added and air is blownin. The -dyestufi, which is isolated in the usual manner, is, when dry, a dark blue powder, scarcely soluble in concentrated sulphuricacid, with a blue coloration and dyes vegetable fibers froni'a sodium sulphide bath fast yellowish green shades.

When starting from the leucoindophenol derived from N-( l-acetylaminophenyl) -1-aminonaphthalene-G-sulphonic acid, a dyestuff' dyeing more bluish shades of good fastness to light is obtained.

Examplefl 20 parts-of the indophenol or leucoindophenol of the formula as-given in-the foregoing example are mixed with an aqueous polysulphidesolution for 46=parts of crystallized sodiumsulphide and-47 parts-of sulphur and 6 parts of copper light is obtained when starting from the leucoindophenol derived from N-(l-acetylaminophenyl)-1-aminonaphthalene-G-sulphonic acid;

Emampleld I '30 parts of the leucoindophenol derived from 4'-acetylaminodiphenyl -1- naphthyIamiho-B-sulphonic acid of the formula:

HOQNH8ZIH-OO-NH-G 0 0H: I i 01H I or of the corresponding indophenol are mixed with anaqueous polysulphide solution prepared from parts of crystallized sodium sulphide and 71 parts of sulphur and 9 parts of copper sul- "phate'and the mixture is boiled for-some time under reflux. Then'the reaction mass is diluted with about 200 parts of water and after addition of about 30 parts of crystallized'sodium sulphide the dyestuif'formed is blown out'with air and isolatedin theusual'manner. It is, whendry, a

greenish black powder soluble in concentrated sul phuric acid with a greenish blue color and dyes vegetable fibers from the sodium sulphide bath bright very yellowish green shades of good fastness properties.

Similar dyestufis are obtained when starting from indophenols or leucoindophenols, the diphenyl radicle of which is substituted by methyl or methoxy groups, or which contain instead of the diphenyl radicle radicles of the naphthalene, diphenylmethane, diphenylamine, diphenylether, diphenylsulphone, carbazole, diphenyleneoxide and anthracene series. For instance, the sulphur dyestufi derived from the leucoindophenol of the compound of the formula:

NHCOCH;

NH SOaH dyes the vegetable fiber greenish blue shades.

We claim: 1. Sulphur dyestufls obtained by acting with an alkali metal polysulphide on a member of the group consisting of a leucoindophenol of the general formula:

wherein R stands for a member of the group consisting of a radicle of the benzene and naphthalene series, R1 for a member of the group consisting of a radicle of the benzene and polynuclear aromatic series, one X for hydrogen and the other X for a member of the group consisting of hydrogen, COOI-I and SOsH, and acyl for a member of the group consisting of lower aliphatic acid radicles and benzene-mono-carboxylic acid radicles, and of a corresponding indophenol, which dyestufis dye the vegetable fibers bright blue to greenish blue to green shades of good fastness, particularly to light.

2. A sulphur dyestufi obtained by acting with an alkali metal polysulphide on the leucoindophenol of the formula:

which dyestuff is, when dry, a blue powder soluble in concentrated sulphuric acid with a blue color and dyes vegetable fibers from a sodium sulphide bath greenish blue shades of good fastness.

, WERNER ZERWECK.

WILHELM HECHTENBERG. 

